Investigating The Synthetic Mechanism Of Energy Compounds By On-line IR Spectroscopy Combined With Independent Component Analysis

There are five parts in this thesis. The development and application of energetic compounds, on-line infrared spectroscopy and independent component analysis (ICA) was overviewed in recent years. The reaction process of3,5-diamino-1,2,4-triazole,4-amino-3,5-dimethyl pyrazole and3-amino-4-amidoximinofuranzan was investigated by ICA and its improved methods, and the chemistry information such as the concentration changes and their IR spectra of intermediates, reactant and product were obtained, it could provide a new research method for investigating synthetic mechanism.In the first chapter, an overview of the application and research of process analysis, on-line infrared spectroscopy combined with chemometrics, and the principle of ICA algorithm and its application and progress in the field of chemistry.In the second chapter, investigating the synthetic mechanism of3,5-diamino-1,2,4-triazole by knerl independent component analysis.On-line FT-IR spectroscopy was employed to monitor the synthetic process of3,5-diamino-1,2,4-triazole from cyanoguanidine and hydrazine dihydrochloride. Four ICA methods such as Fast-ICA, KICA, JADE, MLICA and one MCR-ALS approach were used to directly estimate the IR data matrix, and the spectra and concentration profiles of reactants, intermediates and product were obtained. It found that KICA is the best in comparison with the results of these chemometrics methods, and it needs shorter calculation time and shows higher accuracy. In addition, the intermediates involved in the reaction process were validated by the DFT B3LYP method. It indicates that the results obtained by ICA method are consistent with the calculation results of quantum chemical calculation method. On-line FT-IR spectroscopy combined with KICA method can be applied to investigate the synthetic mechanism of DAT successfully.In the third chapter, investigating the synthetic mechanism of4-amino-3,5-dimethyl pyrazole by knerl independent component analysis.On-line FT-IR spectroscopy was used to monitor the synthetic process of4-amino-3,5-dimethyl pyrazole from hydrazine hydrate and2,3,4-pentanetrione-3-oxime. The IR data matrix was processed by ICA, PCA and WT methods. The spectra and concentration profiles of reactants, intermediates and product were obtained, and these information was used to deduce the synthetic mechanism. Then the intermediates involved in the reaction process were validated by the DFT B3LYP method. It shows that the results obtained by KICA method are in line with the calculation results of quantum chemical calculation method. These results indicate that KICA can be applied to the synthetic mechanism of4-amino-3,5-dimethyl pyrazole.In the fourth chapter, study on the synthetic mechanism of3-amino-4-amidoximinofuranzan by a FastICA-ALS algorithm.On-line FT-IR spectroscopy was used to monitor the synthetic process of3-amino-4-amidoximinofuranzan from methylene cyanide, hydroxylamine hydrochloride and sodium nitrite. The IR data matrix was resolved by FastICA-ALS algorithm. The spectra and concentration profiles of reactants, intermediates and product were obtained, and these information was used to deduce the synthetic mechanism. The experimental results show that the mixed method can process the nonnegative constraints of the concentration of data in the process effectively, which makes data analysis more pratical significance.